Biomedical subjects

Roland Lindh

Publications and source records attributed to Roland Lindh.

6 recordsLinked to original sources

PubMed2006

The prediction of the nuclear quadrupole splitting of 119Sn Mössbauer spectroscopy data by scalar relativistic DFT calculations.

The electric field gradient components for the tin nucleus of 34 tin compounds of experimentally known structures and (119)Sn Mössbauer spectroscopy parameters were computed at the scalar relativistic density functional theory level of approximation. The theoretical values of the electric field gradient components were used to determine a quantity, V, which is proportional to the nuclear quadrupole splitting parameter (DeltaE). In a subsequent linear regression analysis the effective nuclear quadrupole moment, Q, was evaluated. The value of (11.9+/-0.1) fm(2) is a significant improvement over the non-relativistic result of (15.2+/-4.4) fm(2) and is in agreement with the experimental value of (10.9+/-0.8) fm(2). The average mean square error DeltaE(calcd)-DeltaE(exptl)=+/-0.3 mm s(-1) is a factor of two smaller than in the non-relativistic case. Thus, the approach has a quality which provides accurate support for the structure interpretation by (119)Sn spectroscopy. It was noted that geometry optimization at the relativistic level does not significantly increase the quality of the results compared with non-relativistic optimized structures. The accuracy in the approach called on us to consider the singlet-triplet state nature of the electronic structure of one of the investigated compounds.

Journal Article↗

PubMed2006

Spin-orbit ab initio investigation of the photolysis of bromoiodomethane.

The photodissociation of bromoiodomethane has been investigated by spin-orbit ab initio calculations. The experimentally observed A- and B-bands and the corresponding photoproducts were assigned by multistate second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space state interaction potential energy curves, vertical excitation energies, and oscillator strengths of low-lying excited states. The present conclusions with respect to the dissociation process in the B-band are different compared with those of previous studies. The reaction between the iso-CH(2)Br-I and iso-CH(2)I-Br species has also been studied. Finally, a set of stable excited states was identified for both isomers. These species might be of importance in the recombination process that follows the photodissociation in a solvent.

Computer Simulation↗

PubMed2005

New relativistic ANO basis sets for transition metal atoms.

New basis sets of the atomic natural orbital (ANO) type have been developed for the first, second, and third row transition metal atoms. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive and negative ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies, electron affinities, and excitation energies for all atoms and polarizabilities for spherically symmetric atoms. These calculations include spin-orbit coupling using a variation-perturbation approach. Computed ionization energies have an accuracy better than 0.2 eV in most cases. The accuracy of computed electron affinities is the same except in cases where the experimental values are smaller than 0.5 eV. Accurate results are obtained for the polarizabilities of atoms with spherical symmetry. Multiplet levels are presented for some of the third row transition metals.

Journal Article↗

PubMed2005

Computation of conical intersections by using perturbation techniques.

Multiconfigurational second-order perturbation theory, both in its single-state multiconfigurational second-order perturbation theory (CASPT2) and multistate (MS-CASPT2) formulations, is used to search for minima on the crossing seams between different potential energy hypersurfaces of electronic states in several molecular systems. The performance of the procedures is tested and discussed, focusing on the problem of the nonorthogonality of the single-state perturbative solutions. In different cases the obtained structures and energy differences are compared with available complete active space self-consistent field and multireference configuration interaction solutions. Calculations on different state crossings in LiF, formaldehyde, the ethene dimer, and the penta-2,4-dieniminium cation illustrate the discussions. Practical procedures to validate the CASPT2 solutions in polyatomic systems are explored, while it is shown that the application of the MS-CASPT2 procedure is not straightforward and requires a careful analysis of the stability of the results with the quality of the reference wave functions, that is, the size of the active space.

Journal Article↗

PubMed2004

Local properties of quantum chemical systems: the LoProp approach.

A new method is presented, which makes it possible to partition molecular properties like multipole moments and polarizabilities, into atomic and interatomic contributions. The method requires a subdivision of the atomic basis set into occupied and virtual basis functions for each atom in the molecular system. The localization procedure is organized into a series of orthogonalizations of the original basis set, which will have as a final result a localized orthonormal basis set. The new localization procedure is demonstrated to be stable with various basis sets, and to provide physically meaningful localized properties. Transferability of the methyl properties for the alkane series and of the carbon and hydrogen properties for the benzene, naphtalene, and anthracene series is demonstrated.

Journal Article↗

PubMed2004

Analytical energy gradients for local second-order Møller-Plesset perturbation theory using density fitting approximations.

An efficient method to compute analytical energy derivatives for local second-order Møller-Plesset perturbation energy is presented. Density fitting approximations are employed for all 4-index integrals and their derivatives. Using local fitting approximations, quadratic scaling with molecular size and cubic scaling with basis set size for a given molecule is achieved. The density fitting approximations have a negligible effect on the accuracy of optimized equilibrium structures or computed energy differences. The method can be applied to much larger molecules and basis sets than any previous second-order Møller-Plesset gradient program. The efficiency and accuracy of the method is demonstrated for a number of organic molecules as well as for molecular clusters. Examples of geometry optimizations for molecules with 100 atoms and over 2000 basis functions without symmetry are presented.

Journal Article↗